Air-stable, electron-deficient Fe(II) catalytic porphyrins. Characterization and molecular structures of rare high spin Fe(II) hexacoordinated porphyrins.

The synthesis, characterization, and molecular structures of the first air-stable, hexacoordinated high spin Fe(II) porphyrins (1) with axial alcohols are reported (1 = Fe(II) meso-tetrakis(o-dichlorophenyl)-beta-octanitroporphyrin). The structure of 1 with two axial waters is also presented. The very different conformations and metrics observed with the two types of ligands illustrate the acute interplay between ligands, conformations, and spin states in Fe porphyrins.

Reduction and Accumulation of Gold(III) by Medicago sativa Alfalfa Biomass: X-ray Absorption Spectroscopy, pH, and Temperature Dependence.

We report herein the use of Medicago sativa alfalfa shoot biomass for the removal of gold from aqueous solutions. The accumulation process involves the reduction of Au(III) to colloidal Au(0) and is shown to increase at elevated temperatures and at lower pH. X-ray absorption spectroscopy (XAS) was used to determine that gold(III) was reduced to form gold(0) colloids, which varied in size depending on the pH of the initial solution. The gold cluster radius was 6.2 ± 1 Å at pH 5 and 9.0 ± 1 Å at pH 2. Our findings indicate that essentially another layer of gold atoms was deposited onto the colloid surface at pH 2. Possible mechanisms of bioreduction and accumulation are discussed.